Process for trichromatic dyeing or printing

ABSTRACT

A process for dyeing or printing natural or synthetic polyamide fiber material by the trichromatic technique, which comprises using at least one blue-dyeing dye of formula ##STR1## together with at least one red-dyeing dye of formula ##STR2## together with at least one yellow- or orange-dyeing dye of formula ##STR3##

PROCESS FOR TRICHROMATIC DYEING OR PRINTING

The present invention relates to a process for dyeing or printingnatural or synthetic polyamide fibre materials by the trichromatictechnique.

It is the object of this invention to provide a process for dyeing orprinting natural or synthetic polyamide fibre materials with dyessuitable for combination dyeing by the trichromatic technique.

It has now been found that this object can be achieved by the inventiveprocess described hereinafter. The dyeings so obtained meet the aboverequirements and are distinguished in particular by level colourbuild-up while at the same time having consistency of shade at differentconcentrations as well as good compatibility.

The invention relates to a process for dyeing or printing natural orsynthetic polyamide fibre material by the trichromatic technique, whichcomprises using at least one blue-dyeing dye of formula (1) or (2)##STR4## wherein R₁, R₂, R₃ and R₄ are each independently of one anotherhydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido,halogen or sulfo, together with at least one red-dyeing dye of formula(3) ##STR5## wherein R and R' are each independently of the otherhydrogen or unsubstituted or substituted C₁ -C₄ alkyl, R₅, R₆, R₇ and R₈are each independently of one another hydrogen, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₂ -C₄ alkanoylamino, ureido, halogen or sulfo, and X₁ ishalogen, and together with at least one yellow- or orange-dyeing dye offormula (4) or (5) ##STR6## wherein R and R' are each independently ofthe other hydrogen or unsubstituted or substituted C₁ -C₄ alkyl, X₂ andX₃ are halogen, and R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆ are eachindependently of one another hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy,ureido, halogen, sulfo, or C₂ -C₄ alkanoylamino or C₁ -C₄alkoxycarbonyl-amino which may be substituted in the alkyl moiety.

By the trichromatic technique is meant the additive dye blending ofsuitably chosen yellow-, orange-, red- and blue-dyeing dyes with whichany desired shade of the visible colour spectrum may be achieved by theappropriate choice of the quantity ratios of the dyes.

R, R', R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅and R₁₆ defined as C₁ -C₄ alkyl may suitably be methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl or tert-butyl. Methyl or ethyl arepreferred, and methyl is particularly preferred. R and R' defined as C₁-C₄ alkyl may be unsubstituted or substituted by e.g. hydroxy, C₁ -C₄alkoxy, halogen or sulfato. R and R' are preferably unsubstituted.

R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆defined as C₁ -C₄ alkoxy may suitably be methoxy, ethoxy, propoxy,isopropoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy, preferablymethoxy.

R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆defined as C₂ -C₄ alkanoylamino may suitably be propionylamino or,preferably, acetylamino. R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆defined as C₂ -C₄ alkanoylamino may be unsubstituted or, for example,substituted in the alkyl moiety by C₁ -C₄ alkoxy or hydroxy.

R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆ defined as C₁ -C₄alkoxycarbonylamino are preferably methoxycarbonylamino orethoxycarbonylamino. R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆ defined asC₁ -C₄ alkoxycarbonylamino may be unsubstituted or, for example,substituted in the alkyl moiety by C₁ -C₄ alkoxy or hydroxy.

R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆defined as halogen are typically fluoro or bromo and, preferably,chloro.

X₁, X₂ and X₃ are preferably fluoro or chloro. Chloro is preferred.

R and R' are preferably independently of the other hydrogen or C₁ -C₄alkyl. Hydrogen is preferred.

R₁, R₂, R₃ and R₄ are preferably independently of one another hydrogen,C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido or halogen, inparticular hydrogen.

R₅, R₆, R₇ and R₈ are preferably independently of one another hydrogen,C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido or halogen, inparticular hydrogen.

R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆ are preferably independently ofone another hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, ureido, halogen, orC₂ -C₄ alkanoylamino or C₁ -C₄ alkoxycarbonylamino which may besubstituted in the alkyl moiety by C₁ -C₄ alkoxy or hydroxy.

The blue-dyeing dye preferably consists of at least one dye of formula##STR7## wherein R₁, R₂, R₃ and R₄ have the meanings and preferredmeanings cited above, R₁, R₂, R₃ and R₄ preferably being hydrogen.

The blue-dyeing dye particularly preferably consists of at least one dyeof formula (1), more preferably of at least one dye of formula (6).

Interesting blue-dyeing dyes are also mixtures consisting of the dyes offormulae (1) and (2), preferably mixtures consisting of the dyes offormulae (6) and (7). The dye of formula (1) is preferably used in anamount from 5 to 95% by weight, more preferably from 10 to 90% by weightand, particularly preferably, from 20 to 80% by weight, based on thetotal amount of the dyes of formulae (1) and (2). The dye of formula (1)is particularly preferably used in an amount from 40 to 60% by weight.

The red-dyeing dye preferably consists of at least one dye of formula##STR8## wherein R, R', R₅, R₆, R₇, R₈ and X₁ have the meanings andpreferred meanings cited above.

The red-dyeing dye are particularly preferably those of formula (3), inparticular those of formula (8), wherein R and R' are each independentlyof the other hydrogen or C₁ -C₄ alkyl, preferably hydrogen, R₅, R₆, R₇and R₈ are each independently of one another hydrogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido or halogen, preferablyhydrogen, and X₁ is fluoro or, preferably, chloro.

The red-dyeing dye is very particularly preferably that of formula##STR9##

The naphthalene rings of the yellow- or orange-dyeing dyes of formulae(4) and (5) preferably contain only one or two sulfo groups each, morepreferably only one sulfo group each. The total number of sulfo groupsof the dyes of formulae (4) and (5) is preferably 2 to 4 each, morepreferably two.

Preferred yellow- or orange-dyeing dyes of formula (4) are those offormula ##STR10## wherein R, R', R₉, R₁₀, R₁₁, R₁₂ and X₂ have themeanings and preferred meanings cited above.

Particularly preferred yellow- or orange-dyeing dyes of formula (4), andparticularly preferred dyes of formula (10), are those, wherein R and R'are each independently of the other hydrogen or C₁ -C₄ alkyl, preferablyhydrogen, R₉, R₁₀, R₁₁ and R₁₂ are each independently of one anotherhydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, ureido, halogen, or C₂ -C₄alkanoylamino or C₁ -C₄ alkoxycarbonylamino which may be substituted inthe alkyl moiety by C₁ -C₄ alkoxy or hydroxy, R₉ and R₁₁ preferablybeing hydrogen, X₂ is fluoro or, preferably, chloro, the naphthalenerings of the dyes of formula (4) or of formula (10) each containing onlyone or two sulfo groups, preferably only one sulfo group.

Very particularly preferred yellow- or orange-dyeing dyes of formula (4)are those of formula ##STR11## wherein R₁₀ and R₁₂ have the meanings andpreferred meanings cited above. R₁₀ and R₁₂ are preferably hydrogen, C₁-C₄ alkyl, C₁ -C₄ alkoxy, ureido, halogen, or C₂ -C₄ alkanoylamino or C₁-C₄ alkoxycarbonylamino which may be substituted in the alkyl moiety byC₁ -C₄ alkoxy or hydroxy; more preferably C₁ -C₄ alkyl, C₁ -C₄ alkoxy,ureido, halogen, or C₂ -C₄ alkanoylamino or C₁ -C₄ alkoxycarbonylaminowhich may be substituted in the alkyl moiety by C₁ -C₄ alkoxy or hydroxyand, most preferably, ureido.

Preferred yellow- or orange-dyeing dyes of formula (5) are those offormula ##STR12## wherein R, R', R₁₃, R₁₄, R₁₅, R₁₆ and X₃ have themeanings and preferred meanings cited above.

Particularly preferred yellow- or orange-dyeing dyes of formula (5), andparticularly preferred dyes of formula (12), are those, wherein R and R'are each independently of the other hydrogen or C₁ -C₄ alkyl, preferablyhydrogen, R₁₃, R₁₄, R₁₅ and R₁₆ are each independently of one anotherhydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, ureido, halogen, or C₂ -C₄alkanoylamino or C₁ -C₄ alkoxycarbonylamino which may be substituted inthe alkyl moiety by C₁ -C₄ alkoxy or hydroxy, R₁₃ and R₁₅ preferablybeing hydrogen, X₃ if fluoro or, preferably, chloro, the naphthalenerings of the dyes of formula (5) or of formula (12) each containing onlyone or two sulfo groups, preferably only one sulfo group.

Particularly interesting yellow- or orange-dyeing dyes are those offormula (4), preferably those of formula (10) and, more preferably,those of formula (11). Very particularly interesting yellow- ororange-dyeing dyes are those of formula (11), wherein R₁₀ and R₁₂ areureido.

A preferred embodiment of the process of this invention is that whichcomprises using at least one red-dyeing dye of formula (8) together withat least one yellow- or orange-dyeing dye of formula (4), in particularof formula (10) and, preferably, of formula (11). The blue-dyeing dyesof formulae (1) and (2) have the meanings and preferred meanings citedabove. The blue-dyeing dyes preferably consist of at least one dye offormulae (6) and (7), R₁, R₂, R₃ and R₄ preferably being hydrogen.

A particularly preferred embodiment of the process of this invention isthat which comprises using a red-dyeing dye of formula (9) together withat least one yellow- or orange-dyeing dye of formula (4), in particularof formula (10) and, preferably, of formula (11). The blue-dyeing dyesof formulae (1) and (2) have the meanings and preferred meanings citedabove. The blue-dyeing dyes preferably consist of at least one dye offormulae (6) and (7), R₁, R₂, R₃ and R₄ preferably being hydrogen.

A very particularly preferred embodiment of the process of thisinvention is that which comprises using a red-dyeing dye of formula (9)together with a yellow- or orange-dyeing dye of formula (11), whereinR₁₀ and R₁₂ are ureido. The blue-dyeing dyes of formulae (1) and (2)have the meanings and preferred meanings cited above. The blue-dyeingdyes preferably consist of at least one dye of formulae (6) and (7), R₁,R₂, R₃ and R₄ preferably being hydrogen. The dye of formula (6) is ofvery particular interest.

Another interesting embodiment of the novel process relates to thepreparation of black shades. In this case the dyes of formulae (1)and/or (2) are conveniently used in an amount from 30 to 70% by weight,preferably from 40 to 60% by weight; the dyes of formula (3) areconveniently used in an amount from 3 to 20% by weight, preferably from5 to 15% by weight, and the dyes of formulae (4) and/or (5) areconveniently used in an amount from 30 to 50% by weight, preferably from35 to 45% by weight. These amounts are all based on the total amount ofthe dyes of formulae (1) to (5). Accordingly, the sum of the amounts ofthe dyes of formulae (1) to (5) employed is 100% by weight.

The invention also relates to dye mixtures, comprising a mixture of atleast one blue-dyeing dye of formula (1) or (2), together with at leastone red-dyeing dye of formula (3), and together with at least oneyellow- or orange-dyeing dye of formula (4) or (5). The dyes of formulae(1), (2), (3), (4) and (5) and the mixtures thereof have the meaningsand preferred meanings cited above.

The dyes of formulae (1), (2), (3), (4) and (5) are known or can beprepared in general analogy to known dyes. The dyes of formulae (1) and(2), for example, can be obtained according to the instructions of U.S.Pat. No. 4,009,156 and U.S. Pat. No. 4,591,634.

The dyes of formula (3) can, for example, be obtained by condensingcyanuric halide with the amines of formulae ##STR13##

The dyes of formula (4) can, for example, be obtained by condensingcyanuric halide with the amines of formulae ##STR14##

The dyes of formula (5) can, for example, be obtained by condensingcyanuric halide with the amines of formulae ##STR15##

The cyanuric halide is preferably first reacted with aboutstoichiometric amounts of one of the two aminoazo compounds at atemperature of -5 to 20° C., the pH being kept in the range from neutralto slightly acid, preferably from 5 to 7, by the addition of suitablebases, typically alkali metal bases such as lithium hydroxide, sodiumhydroxide or potassium hydroxide, or lithium carbonate, sodium carbonateor potassium carbonate. The triazine derivative so obtained can beseparated off, or the reaction mixture can be used direct for a furtherreaction. Conveniently about stoichiometric amounts of the other of thetwo aminoazo compounds are added to the reaction mixture so obtained, orto the triazine derivative previously separated off, and are reactedwith the triazine derivative at slightly elevated temperature,preferably from 30 to 50° C., and at a neutral to slightly acid pH ofpreferably 6 to 7. If the two aminoazo compounds are identical, about 2equivalents of this aminoazo dye are reacted with 1 equivalent ofcyanuric halide, the temperature preferably being at first kept at -5 to20° C. and then raised to about 30 to 50° C.

The aminoazo compounds are known or can be prepared in general analogyto known compounds. These azo compounds can, for example, be obtained bycustomary diazotisation and coupling reactions.

Diazotisation is usually effected with a nitrite, e.g. an alkali metalnitrite such as sodium nitrite, and in a medium containing mineral acid,conveniently hydrochloric acid, in the temperature range from e.g. -5 to30° C. and, preferably, from 0 to 10° C.

Coupling is usually carried out in the acid, neutral or weakly alkalinepH range and in the temperature range from e.g. -5 to 30° C., preferablyfrom 0 to 25° C.

The dyes employed in the novel process for trichromatic dyeing orprinting are either in the form of their free sulfonic acids or,preferably, in the from of their salts.

Examples of suitable salts are the alkali metal salts, alkaline earthmetal salts or ammonium salts, or the salts of an organic amine. Typicalexamples are the sodium, lithium, potassium or ammonium salts or thesalt of mono-, di- or triethanolamine.

The dyes employed in the process of this invention may contain furtherauxiliaries, such as sodium chloride or dextrin.

The trichromatic dyeing or printing process of this invention may beapplied in conventional dyeing or printing methods. In addition tocontaining water and the dyes, the dye liquors or printing pastes maycontain further auxiliaries, for example wetting agents, antifoams,levelling agents or agents which influence the property of the textilematerials, e.g. softeners, flameproofing additives, or dirt, water andoil repellents, as well as water softeners and natural or syntheticthickeners, e.g. alginates and cellulose ethers.

The novel process for trichromatic dyeing or printing is also suitablefor dyeing from short liquors, e.g. in continuous dyeing or in batchwiseor continuous foam dyeing processes.

The amounts of the individual dyes employed in the dye liquors orprinting pastes may vary within wide limits depending on the desiredtinctorial strenght. Convenient amounts have been found to be usuallythose from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight,based on the goods to be dyed or on the printing paste.

Dyeing is preferably carried out by the exhaust process.

The goods are preferably dyed at a pH from 3 to 7, more preferably from3 to 5. The liquor ratio may be chosen from a wide range, typically from1:5 to 1:50, preferably from 1:5 to 1:30. Dyeing is preferably carriedout in the temperature range from 70 to 110° C., more preferably from 80to 105° C.

In trichromatic dyeing or printing, the dyes employed in the process ofthis invention are distinguished by level colour build-up, goodexhaustion properties, good consistency of shade even at differentconcentrations, good fastness properties and solubility and, inparticular, by very good compatibility.

The novel process for trichromatic dyeing or printing is suitable fordyeing or printing natural polyamide materials, e.g. wool, and also, inparticular, synthetic polyamide materials, e.g. polyamide 6 or polyamide66, and is suitable for dyeing or printing wool and synthetic polamideblends and yarns.

The textile material may be in any form of presentation, e.g. in theform of fibre, yarn, wovens, knits or carpets.

The dyeings obtained are level and have good allround fastnessproperties, in particular good fastness to rubbing, wet rubbing andlight.

In the following Examples, parts are by weight and temperatures aregiven in degrees Celsius. The relationship between parts by weight andparts by volume is the same as that between the gram and the cubiccentimetre.

EXAMPLE 1

200 parts of demineralised water are adjusted to a pH of 3.5 with aceticacid at room temperature. To this bath is then added a mixture of 1 partof a dye which, in the form of the free acid, corresponds to thecompound of formula ##STR16## 0.19 part of a dye which, in the form ofthe free acid, corresponds to the compound of formula ##STR17## and 0.8part of a dye which, in the form of the free acid, corresponds to thecompound of formula ##STR18## 10 parts of polyamide 66 fibre material(Helanca tricot) are put into the resultant dye solution and the dyebathis heated over 45 minutes to about 100° C. The dyebath is kept at thistemperature for 60 minutes and then cooled to 70° C. The dyed goods areremoved from the dyebath, rinsed with water and then dried, giving afabric dyed in a black shade.

What is claimed is:
 1. A process for dyeing or printing natural orsynthetic polyamide fibre material by the trichromatic technique, whichcomprises using at least one blue-dyeing dye of formula (1) ##STR19##wherein R₁, R₂, R₃ and R₄ are each independently of one anotherhydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido orhalogen, together with at least one red-dyeing dye of formula (3)##STR20## wherein R and R' are each independently of the other hydrogenor C₁ -C₄ alkyl which is unsubstituted or substituted by hydroxy, C₁ -C₄alkoxy, halogen or sulfato, R₅, R₆, R₇ and R₈ are each independently ofone another hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino,ureido or halogen, and X₁ is halogen, and together with at least oneyellow- or orange-dyeing dye of formula (4) or (5) ##STR21## wherein Rand R' are each independently of the other hydrogen or C₁ -C₄ alkylwhich is unsubstituted or substituted by hydroxy, C₁ -C₄ alkoxy, halogenor sulfato, X₂ and X₃ are halogen, and R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅and R₁₆ are each independently of one another hydrogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy, uriedo, halogen or C₂ -C₄ alkanoylamino or C₁ -C₄alkoxycarbonylamino which may be substituted in the alkyl moiety by C₁-C₄ alkoxy or hydroxy.
 2. A process according to claim 1, whichcomprises using as blue-dyeing dye at least one dye of formula ##STR22##wherein R₁, R₂, R₃ and R₄ have the meanings claimed in claim
 1. 3. Aprocess according to claim 1, wherein R₁, R₂, R₃ and R₄ are hydrogen. 4.A process according to claim 1, which comprises using as red-dyeing dyeat least one dye of formula ##STR23## wherein R, R', R₅, R₆, R₇, R₈ andX₁ have the meanings claimed in claim
 1. 5. A process according to claim1, which comprises dyeing or printing wool or synthetic polyamide fibrematerial.
 6. A process according to claim 1, wherein R₅, R₆, R₇ and R₈are hydrogen.
 7. A process according to claim 1, which comprises usingas yellow- or orange-dyeing dye at least one dye of formula ##STR24##wherein R, R', R₉, R₁₀, R₁₁, R₁₂ and X₂ have the meanings claimed inclaim
 1. 8. A process according to claim 5, which comprises dyeing orprinting synthetic polyamide fibre material.
 9. A process according toclaim 1, wherein R and R' are hydrogen.
 10. A process according to claim1, wherein X₁, X₂ and X₃ are chloro.
 11. A process according to claim 1,which comprises using as red-dyeing dye a dye of formula ##STR25## andas yellow- or orange-dyeing dye at least one dye of formula ##STR26##wherein R₁₀ and R₁₂ are each independently of the other hydrogen, C₁ -C₄alkyl, C₁ -C₄ alkoxy, ureido, halogen, or C₂ -C₄ alkanoylamino or C₁ -C₄alkoxycarbonylamino which may be substituted in the alkyl moiety by C₁-C₄ alkoxy or hydroxy.
 12. A process according to claim 11, wherein R₁₀and R₁₂ are ureido.
 13. A dye mixture, comprising at least oneblue-dyeing dye of formula (1) ##STR27## wherein R₁, R₂, R₃ and R₄ areeach independently of one another hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy,C₂ -C₄ alkanoylamino, ureido or halogen, together with at least onered-dyeing dye of formula (3) ##STR28## wherein R and R' are eachindependently of the other hydrogen or C₁ -C₄ alkyl which isunsubstituted or substituted by hydroxy, C₁ -C₄ alkoxy, halogen orsulfato, R₅, R₆, R₇ and R₈ are each independently of one anotherhydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido orhalogen, and X₁ is halogen, and together with at least one yellow- ororange-dyeing dye of formula (4) or (5) ##STR29## wherein R and R' areeach independently of the other hydrogen or C₁ -C₄ alkyl which isunsubstituted or substituted by hydroxy, C₁ -C₄ alkoxy, halogen orsulfato, X₂ and X₃ are halogen, and R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ andR₁₆ are each independently of one another hydrogen, C₁ -C₄ alkyl, C₁ -C₄alkoxy, ureido, halogen or C₂ -C₄ alkanoylamino or C₁ -C₄alkoxycarbonylamino which may be substituted in the alkyl moiety by C₁-C₄ alkoxy or hydroxy.